Low molecular weight ethylene interpolymers and polymerization process

ABSTRACT

Low molecular weight olefin polymers are prepared by a polymerization process employing titanium complexes comprising a 3-aryl-substituted cyclopentadienyl ring or substituted derivatives thereof as polymerization catalysts.

CROSS REFERENCE STATEMENT

This application is a continuation in part of application U.S. Ser. No.10/123,277, filed Apr. 15, 2002, now U.S. Pat. No. 6,829,147 whichclaims the benefit of U.S. Provisional Application No. 60/290,696, filedMay 14, 2001, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to Group 4 metal complexes containing an arylsubstituted cyclopentadienyl ligand and to polymerization catalystsderived from such complexes that are particularly suitable for use in apolymerization process for preparing homopolymers and copolymers ofolefins or diolefins, including copolymers comprising two or moreolefins or diolefins such as copolymers comprising a monovinyl aromaticmonomer and ethylene.

Constrained geometry metal complexes and methods for their preparationare disclosed in U.S. Pat. No. 5,703,187. This publication also teachesthe preparation of certain novel copolymers of ethylene and a hinderedvinyl monomer, including monovinyl aromatic monomers, having apseudo-random incorporation of the hindered vinyl monomer therein.Additional teachings of constrained geometry catalysts may be found inU.S. Pat. Nos. 5,321,106, 5,721,185, 5,374,696, 5,470,993, 5,541,349,and 5,486,632, WO97/15583, WO97/19463.

In Table 1 of U.S. Pat. No. 5,723,560 and related patents,tetraphenylcyclopentadienyl-, 3,4-diphenylcyclopentadienyl-, and2,5-diphenylcyclopentadienyl-ligands are listed. 2- and/or 3-substitutedindenyl metal complexes are disclosed in U.S. Pat. No. 6,015,868.3-Aryl-substituted indenyl metal complexes are disclosed in U.S. Pat.No. 5,866,704. Certain highly active, polyaromatic, metal complexes,especially derivatives of s-indacenyl- andcyclopentaphenanthrenyl-ligand groups are disclosed in U.S. Pat. No.5,965,756 and U.S. Ser. No. 09/122,958, filed Jul. 27, 1998,(WO99/14221, published Mar. 25, 1999) respectively. Despite the advancein the art occasioned by the foregoing metal complexes, improved metalcomplexes that are capable of producing high styrene contentethylene/styrene interpolymers (ESI) and that are economical to prepareare continually desired. Accordingly, it would be desirable if therewere provided metal complexes having acceptable catalytic propertiesthat are also economical to produce.

SUMMARY OF THE INVENTION

According to the present invention there is provided3-arylcyclopentadienyl-substituted metal complexes corresponding to theformula:

wherein,

Ar is an aryl group of from 6 to 30 atoms not counting hydrogen;

R independently each occurrence is hydrogen, Ar, or a group other thanAr selected from hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl,halide, hydrocarbyloxy, trihydrocarbylsiloxy,bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino,hydrocarbadiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino,hydrocarbadiylphosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R group having up to 40atoms not counting hydrogen atoms;

M is titanium;

Z′ is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂,BR⁶, BR⁶L″, or GeR⁶ ₂;

Y is —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂;

R⁵, independently each occurrence, is hydrocarbyl, trihydrocarbylsilyl,or trihydrocarbylsilylhydrocarbyl, said R⁵ having up to 20 atoms otherthan hydrogen, and optionally two R⁵ groups or R⁵ together with Y form aring system;

R⁶, independently each occurrence, is hydrogen, or a member selectedfrom hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenatedaryl, —NR⁵ ₂, and combinations thereof, said R⁶ having up to 20non-hydrogen atoms, and optionally, two R⁶ groups form a ring system;

L″ is a monodentate or polydentate Lewis base optionally bonded to R⁶;

X is hydrogen or a monovalent anionic ligand group having up to 60 atomsnot counting hydrogen;

L independently each occurrence is a neutral ligating compound having upto 20 atoms, other than hydrogen, and optionally L and X are bondedtogether;

X′ is a divalent anionic ligand group having up to 60 atoms other thanhydrogen;

z is 0, 1 or 2;

x is 0, 1, 2, or 3;

l is a number from 0 to 2, and

x′ is 0 or 1.

The above compounds may exist as isolated crystals, as a mixture withother compounds, in the form of a solvated adduct, dissolved in asolvent, especially an organic liquid solvent, or in the form of adimer.

Also, according to the present invention, there is provided a catalystfor polymerization of one or more addition polymerizable monomerscomprising:

A. i) a metal complex of formula I, and

ii) an activating cocatalyst,

the molar ratio of i) to ii) being from 1:10,000 to 100:1, or

B. the reaction product formed by converting a metal complex of formulaI to an active catalyst by use of the foregoing activating cocatalyst oran activating technique.

Further according to the present invention there is provided a processfor the polymerization of one or more addition polymerizable monomerscomprising contacting one or more such monomers, especially one or moreC₂₋₂₀ olefins, including cyclic olefins, under polymerization conditionswith a catalyst comprising:

A. i) a metal complex of formula I, and

ii) an activating cocatalyst,

the molar ratio of i) to ii) being from 1:10,000 to 100:1, or

B. the reaction product formed by converting a metal complex of formulaI to an active catalyst by use of the foregoing activating cocatalyst oran activating technique.

Use of the present catalysts and processes is especially efficient inproduction of copolymers of two or more olefins, in particular,copolymers of ethylene and a vinylaromatic monomer, such as styrene, andinterpolymers of three or more polymerizable monomers, including avinylaromatic monomer over a wide range of polymerization conditions,and especially at elevated temperatures. They are especially useful forthe formation of copolymers of ethylene and vinylaromatic monomers suchas styrene (ES polymers), copolymers of ethylene, styrene, and a diene(ESDM polymers), and copolymers of ethylene, propylene and styrene (EPSpolymers). Examples of suitable diene monomers includeethylidenenorbornene, 1,4-hexadiene or similar conjugated ornonconjugated dienes.

The catalysts of this invention may also be supported on a solid,particulated support material and used in the polymerization of additionpolymerizable monomers, especially olefins, in a slurry or in a gasphase process. The catalyst may be prepolymerized with one or moreolefin monomers in situ in a polymerization reactor or in a separateprocess with intermediate recovery of the prepolymerized catalyst priorto the primary polymerization process. Because the metal complexes donot contain fused aromatic rings, they are especially suited for use inthe formation of polymer products having desirable biological response,taste, odor, and organoleptic properties, due to an absence of suchpolycyclic aromatic functionality.

DETAILED DESCRIPTION OF THE INVENTION

All reference to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 1999. Also, any reference to a Group or Groups shall be tothe Group or Groups as reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. For purposes ofnomenclature herein, ring positions on the cyclopentadienyl ring arenumbered beginning with the carbon attached to Z′. For purposes ofUnited States patent practice, the contents of any patent, patentapplication or publication mentioned herein are hereby incorporated byreference in their entirety herein, especially with respect to thedisclosure of organometallic structures, synthetic techniques andgeneral knowledge in the art. As used herein the term “aromatic” or“aryl” refers to a polyatomic, cyclic, ring system containing (4δ+2)π-electrons, wherein δ is an integer greater than or equal to 1.

In the metal complexes, preferred L and L″ groups are carbon monoxide;phosphines, especially trimethylphosphine, triethylphosphine,triphenylphosphine and bis(1,2-dimethylphosphino)ethane; P(OR⁴)₃,wherein R⁴ is C₁₋₂₀ hydrocarbyl; ethers, especially tetrahydrofuran;amines, especially pyridine, bipyridine, tetramethylethylenediamine(TMEDA), and triethylamine; olefins; and neutral conjugated dieneshaving from 4 to 40, preferably 5 to 40 carbon atoms. Complexesincluding neutral diene L groups and no X or X′ groups are those whereinthe metal is in the +2 formal oxidation state.

Further in reference to the metal complexes, X preferably is selectedfrom the group consisting of hydro, halo, hydrocarbyl, silyl, andN,N-dialkylamino-substituted hydrocarbyl. The number of X groups dependson the oxidation state of M, whether Y is divalent or not and whetherany neutral diene groups or divalent X′ groups are present. The skilledartisan will appreciate that the quantity of the various substituentsand the identity of Z′Y are chosen to provide charge balance, therebyresulting in a neutral metal complex. For example, when Z′Y is divalent,and x is zero, x′ is two less than the formal oxidation state of M. WhenZ′Y contains one neutral two electron coordinate-covalent bonding site,and M is in a formal oxidation state of +3, x may equal zero and x′equal 1, or x may equal 2 and x′ equal zero. In a final example, if M isin a formal oxidation state of +2, Z′Y may be a divalent ligand group,whereupon x and x′ are both equal to zero and one neutral L ligand groupmay be present.

Suitable Ar groups for use herein include aromatic hydrocarbyl groups,or aromatic groups containing nitrogen, oxygen, boron, silicon,phosphorus and/or sulfur in a ring thereof in addition to carbon, aswell as di(C₁₋₁₀ hydrocarbyl)amino-, (C₁₋₂₀hydrocarbadiyl)amino-, C₁₋₁₀hydrocarbyloxy-, and tri(C₁₋₁₀ hydrocarbyl)silane- substitutedderivatives thereof. Examples include phenyl, tolyl (all isomers),ethylphenyl (all isomers), trimethylphenyl (all isomers), methoxyphenyl(all isomers), N,N-dimethylaminophenyl (all isomers),trimethylsilylphenyl (all isomers), naphthyl, 4-bisphenyl, pyrrol-1-yl,and 1-methylpyrrol-3-yl.

Preferred compounds of the invention correspond to the formula I whereinindependently each occurrence:

Ar is phenyl, naphthyl, 4-bisphenyl, 3-(N,N-dimethylamino)phenyl,4-methoxyphenyl, 4-methylphenyl, pyrrol-1-yl, or 1-methylpyrrol-3-yl;

R is hydrogen, methyl or Ar;

X is chloride, methyl or benzyl;

X′ is 2,3-dimethyl-1,3-butenediyl;

L is 1,3-pentadiene or 1,4-diphenyl-1,3-butadiene;

Y is —NR⁵—;

Z′ is SiR⁶ ₂;

R⁵ each occurrence is independently hydrocarbyl;

R⁶ each occurrence is independently methyl;

x is 0 or 2;

l is 0 or 1; and

x′ is 0 or 1;

with the proviso that:

when x is 2, x′ is zero, and M is in the +4 formal oxidation state,

when x is 0 and x′ is 1, M is in the +4 formal oxidation state, and

when x and x′ are both 0, 1 is 1, and M is in the +2 formal oxidationstate.

More preferably, R in at least one additional occurrence, is selectedfrom the group consisting of Ar. Highly preferably, at least one of theforegoing additional Ar groups is attached to the 4-position of thecyclopentadienyl ring. Most highly preferably the metal complexes aresubstituted at both the 3- and 4-positions with an Ar group.

Examples of suitable metal complexes according to the present inventionare:

-   (3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-(pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(pyrrol-1-yl)cyclopentadien-1-yl))dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,3-pentadiene;-   (3-(3-N,N-dimethylamino)phenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(3-N,N-dimethylamino)phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(3-N,N-dimethylamino)phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-(4-methoxyphenyl)-4-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(4-methoxyphenyl)-4-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-4-methoxyphenyl)-4-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenyl-4-(N,N-dimethylamnino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silane    titanium dichloride,-   ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silane    titanium dimethyl,-   ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylarmido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl, and-   (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene.

The complexes are rendered catalytically active by combination with anactivating cocatalyst or use of an activating technique, such as thosethat are previously known in the art for use with Group 4 metal olefinpolymerization complexes. Suitable activating cocatalysts for use hereininclude polymeric or oligomeric alumoxanes, especially methylalumoxane,triisobutyl aluminum modified methylalumoxane, or isobutylalumoxane;neutral Lewis acids, such as C₁₋₃₀ hydrocarbyl substituted Group 13compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boroncompounds and halogenated (including perhalogenated) derivativesthereof, having from 1 to 10 carbons in each hydrocarbyl or halogenatedhydrocarbyl group, more especially perfluorinated tri(aryl)boroncompounds, and most especially tris(pentafluorophenyl)borane;nonpolymeric, compatible, noncoordinating, ion forming compounds(including the use of such compounds under oxidizing conditions),especially the use of ammonium-, phosphonium-, oxonium-, carbonium-,silylium- or sulfonium-salts of compatible, noncoordinating anions, orferrocenium salts of compatible, noncoordinating anions; bulkelectrolysis (explained in more detail hereinafter); and combinations ofthe foregoing activating cocatalysts and techniques. A preferred ionforming compound is a tri(C₁₋₂₀-hydrocarbyl)ammonium salt of atetrakis(fluoroaryl)borate, especially atetrakis(pentafluorophenyl)borate. The foregoing activating cocatalystsand activating techniques have been previously taught with respect todifferent metal complexes in the following references: EP-A-277,003,U.S. Pat. Nos. 5,153,157, 5,064,802, 5,321,106, 5,721,185, 5,350,723,5,425,872, 5,625,087, 5,883,204, 5,919,983, 5,783,512, WO 99/15534, andU.S. Ser. No. 09/251,664, filed Feb. 17, 1999 (WO99/42467).

Combinations of neutral Lewis acids, especially the combination of atrialkylaluminum compound having from 1 to 4 carbons in each alkyl groupand a halogenated tri(hydrocarbyl)boron compound having from 1 to 20carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxaneare especially desirable activating cocatalysts. Preferred molar ratiosof Group 4 metal complex: tris(pentafluorophenyl)borane: alumoxane arefrom 1:1:1 to 1:10:30, more preferably from 1:1:1.5 to 1:5:10.

Suitable ion forming compounds useful as cocatalysts in one embodimentof the present invention comprise a cation which is a Brønsted acidcapable of donating a proton, and a compatible, noncoordinating anion,A⁻. As used herein, the term “noncoordinating” means an anion orsubstance which either does not coordinate to the Group 4 metalcontaining precursor complex and the catalytic derivative derivedtherefrom, or which is only weakly coordinated to such complexes therebyremaining sufficiently labile to be displaced by a neutral Lewis base. Anoncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gallium, niobium or tantalum. Suitablemetalloids include, but are not limited to, boron, phosphorus, andsilicon. Compounds containing anions which comprise coordinationcomplexes containing a single metal or metalloid atom are, of course,well known and many, particularly such compounds containing a singleboron atom in the anion portion, are available commercially.

Preferably such cocatalysts may be represented by the following generalformula:(L*-H)_(d) ⁺(A)^(d−)

wherein:

L* is a neutral Lewis base;

(L*-H)⁺ is a conjugate Brønsted acid of L*;

A^(d−) is a noncoordinating, compatible anion having a charge of d−, and

d is an integer from 1 to 3.

More preferably A^(d−) corresponds to the formula:[M′Q₄]⁻;wherein:

M′ is boron or aluminum in the +3 formal oxidation state; and

Q independently each occurrence is selected from hydride, dialkylamido,halide, hydrocarbyl, hydrocarbyloxide, halo-substituted hydrocarbyl,halo-substituted hydrocarbyloxy, and halo-substituted silylhydrocarbylradicals (including perhalogenated hydrocarbyl-perhalogenatedhydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Qhaving up to 20 carbons with the proviso that in not more than oneoccurrence is Q halide. Examples of suitable hydrocarbyloxide Q groupsare disclosed in U.S. Pat. 5,296,433.

In a more preferred embodiment, d is one, that is, the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of catalysts ofthis invention may be represented by the following general formula:(L*-H)⁺(BQ₄)⁻;

wherein:

L* is as previously defined;

B is boron in a formal oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorohydrocarbyl-,fluorohydrocarbyloxy-, hydroxyfluorohydrocarbyl-,dihydrocarbylaluminumoxyfluorohydrocarbyl-, or fluorinatedsilylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the provisothat in not more than one occasion is Q hydrocarbyl. Most preferably, Qis each occurrence a fluorinated aryl group, especially, apentafluorophenyl group.

Preferred Lewis base salts are ammonium salts, more preferablytrialkyl-ammonium- or dialkylarylammonium-salts containing one or moreC₁₂₋₄₀ alkyl groups. The latter cocatalysts have been found to beparticularly suitable for use in combination with not only the presentmetal complexes but other Group 4 metallocenes as well.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention (as well as previously known Group 4 metalcatalysts) are

tri-substituted ammonium salts such as:

-   trimethylammonium tetrakis(pentafluorophenyl) borate,-   triethylammonium tetrakis(pentafluorophenyl) borate,-   tripropylammonium tetrakis(pentafluorophenyl) borate,-   tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate,-   tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate,-   N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,-   N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate,-   N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate,-   N,N-dimethylanilinium    tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl) borate,-   N,N-dimethylanilinium    tetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl) borate,-   N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)    borate,-   N,N-diethylanilinium tetrakis(pentafluorophenyl) borate,-   N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)    borate,-   dimethyltetradecylammonium tetrakis(pentafluorophenyl) borate,-   dimethylhexadecylammonium tetrakis(pentafluorophenyl) borate,-   dimethyloctadecylammonium tetrakis(pentafluorophenyl) borate,-   methylditetradecylammonium tetrakis(pentafluorophenyl) borate,-   methylditetradecylammonium (hydroxyphenyl)tris(pentafluorophenyl)    borate,-   methylditetradecylammonium    (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,-   methyldihexadecylammonium tetrakis(pentafluorophenyl) borate,-   methyldihexadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)    borate,-   methyldihexadecylammonium    (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,-   methyldioctadecylammonium tetrakis(pentafluorophenyl) borate,-   methyldioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)    borate,-   methyldioctadecylammonium    (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,-   methyldioctadecylammonium tetrakis(pentafluorophenyl) borate,-   phenyldioctadecylammonium tetrakis(pentafluorophenyl) borate,-   phenyldioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)    borate,-   phenyldioctadecylammonium    (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,-   (2,4,6-trimethylphenyl)dioctadecylammonium    tetrakis(pentafluorophenyl) borate,-   (2,4,6-trimethylphenyl)dioctadecylammonium    (hydroxyphenyl)tris(pentafluorophenyl)-borate,-   (2,4,6-trimethylphenyl)dioctadecylammonium (diethylaluminoxyphenyl)    tris(pentafluorophenyl)borate,-   (2,4,6-trifluorophenyl)dioctadecylammnonium    tetrakis(pentafluorophenyl)borate,-   (2,4,6-trifluorophenyl)dioctadecylammonium    (hydroxyphenyl)tris(pentafluorophenyl)-borate,-   (2,4,6-trifluorophenyl)dioctadecylammonium    (diethylaluminoxyphenyl)tris(pentafluoro-phenyl) borate,-   (pentafluorophenyl)dioctadecylammonium    tetrakis(pentafluorophenyl)borate,-   (pentafluorophenyl)dioctadecylammonium    (hydroxyphenyl)tris(pentafluorophenyl)-borate,-   (pentafluorophenyl)dioctadecylammonium    (diethylaluminoxyphenyl)tris(pentafluoro-phenyl) borate,-   (p-trifluoromethylphenyl)dioctadecylammonium    tetrakis(pentafluorophenyl)borate,-   (p-trifluoromethylphenyl)dioctadecylammonium    (hydroxyphenyl)tris(pentafluoro-phenyl) borate,-   (p-trifluoromethylphenyl)dioctadecylammonium    (diethylaluminoxyphenyl)tris(penta-fluorophenyl) borate,-   p-nitrophenyldioctadecylammonium tetrakis(pentafluorophenyl)borate,-   p-nitrophenyldioctadecylammonium    (hydroxyphenyl)tris(pentafluorophenyl) borate,-   p-nitrophenyldioctadecylammonium    (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,    and mixtures of the foregoing,

dialkyl ammonium salts such as:

di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate,

-   methyloctadecylammonium tetrakis(pentafluorophenyl) borate,-   methyloctadodecylammonium tetrakis(pentafluorophenyl) borate, and-   dioctadecylammonium tetrakis(pentafluorophenyl) borate;

tri-substituted phosphonium salts such as:

triphenylphosphonium tetrakis(pentafluorophenyl) borate,

-   methyldioctadecylphosphonium tetrakis(pentafluorophenyl) borate, and-   tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)    borate;

di-substituted oxonium salts such as:

diphenyloxonium tetrakis(pentafluorophenyl) borate,

-   di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, and-   di(octadecyl)oxonium tetrakis(pentafluorophenyl) borate;

di-substituted sulfonium salts such as:

-   di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and-   methylcotadecylsulfonium tetrakis(pentafluorophenyl) borate.

Preferred trialkylarnmonium cations are methyldioctadecylammonium anddimethyloctadecylammonium. The use of the above Brønsted acid salts asactivating cocatalysts for addition polymerization catalysts is known inthe art, having been disclosed in U.S. Pat. Nos. 5,064,802, 5,919,983,5,783,512 and elsewhere. Preferred dialkylarylammonium cations arefluorophenyldioctadecylammonium-, perfluoro-phenyldioctacecylammonium-and p-trifluoromethylphenyldi(octadecyl)ammonium cations. It should benoted that certain of the cocatalysts, especially those containing ahydroxyphenyl ligand in the borate anion, may require the addition of aLewis acid, especially a trialkylaluminum compound, to thepolymerization mixture or the catalyst composition, in order to form theactive catalyst composition.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(Ox^(e+))_(d)(A^(d−))_(e).

wherein:

Ox^(e+) is a cationic oxidizing agent having a charge of e+;

e is an integer from 1 to 3; and

A^(d−) and d are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag^(+′) or Pb⁺². Preferredembodiments of A^(d−) are those anions previously defined with respectto the Brønsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate. The use of the above salts asactivating cocatalysts for addition polymerization catalysts is known inthe art, having been disclosed in U.S. Pat. No. 5,321,106.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the formula:{circle around (c)}⁺A⁻

wherein:

{circle around (c)}⁺ is a C₁₋₂₀ carbenium ion; and

A⁻ is as previously defined. A preferred carbenium ion is the tritylcation, that is triphenylmethylium. The use of the above carbenium saltsas activating cocatalysts for addition polymerization catalysts is knownin the art, having been disclosed in U.S. Pat. No. 5,350,723.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:R³ ₃Si(X′)_(q) ⁺A⁻

wherein:

R³ is C₁₋₁₀ hydrocarbyl, and X′, q and A⁻ are as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilyliumtetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.The use of the above silylium salts as activating cocatalysts foraddition polymerization catalysts is known in the art, having beendisclosed in U.S. Pat. No. 5,625,087.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators andmay be used according to the present invention. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433.

Another class of suitable catalyst activators are expanded anioniccompounds corresponding to the formula:(A^(1+a) ¹ )_(b) ₁ (Z¹J¹ _(j) ₁ )^(31 c1) _(d) ₁ ,

wherein:

A¹ is a cation of charge +a¹,

Z¹ is an anion group of from 1 to 50, preferably 1 to 30 atoms, notcounting hydrogen atoms, further containing two or more Lewis basesites;

J¹ independently each occurrence is a Lewis acid coordinated to at leastone Lewis base site of Z¹, and optionally two or more such J¹ groups maybe joined together in a moiety having multiple Lewis acidicfunctionality,

j¹ is a number from 2 to 12 and

a¹, b¹, c¹, and d¹ are integers from 1 to 3, with the proviso that a¹×b¹is equal to c¹×d¹.

The foregoing cocatalysts (illustrated by those having imidazolide,substituted imidazolide, imidazolinide, substituted imidazolinide,benzimidazolide, or substituted benzimidazolide anions) may be depictedschematically as follows:

wherein:

A¹⁺ is a monovalent cation as previously defined, and preferably is atrihydrocarbyl ammonium cation, most preferably containing one or twoC₁₀₋₄₀ alkyl groups, especially the methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium-cation,

R⁸, independently each occurrence, is hydrogen or a halo, hydrocarbyl,halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (includingmono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms notcounting hydrogen, preferably C₁₋₂₀ alkyl, and

J¹ is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)aluminane.

Examples of these catalyst activators include thetrihydrocarbylammonium-, especially, methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium-salts of:

-   bis(tris(pentafluorophenyl)borane)imidazolide,-   bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,    bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide,    bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,-   bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,-   bis(tris(pentafluorophenyl)borane)imidazolinide,-   bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,    bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,    bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,-   bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,-   bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,-   bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,-   bis(tris(pentafluorophenyl)alumane)imidazolide,-   bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,    bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,    bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,-   bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,-   bis(tris(pentafluorophenyl)alumane)imidazolinide,-   bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,    bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,    bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,-   bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide,-   bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, and-   bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

A further class of suitable activating cocatalysts include cationicGroup 13 salts corresponding to the formula:[M″Q¹ ₂L′_(1′)]⁺(Ar^(f) ₃M′Q²)⁻

wherein:

M″ is aluminum, gallium, or indium;

M′ is boron or aluminum;

Q¹ is C₁₋₂₀ hydrocarbyl, optionally substituted with one or more groupswhich independently each occurrence are hydrocarbyloxy,hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino,hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, orhydrocarbylsulfido groups having from 1 to 20 atoms other than hydrogen,or, optionally, two or more Q¹ groups may be covalently linked with eachother to form one or more fused rings or ring systems;

Q² is an alkyl group, optionally substituted with one or more cycloalkylor aryl groups, said Q² having from 1 to 30 carbons;

L′ is a monodentate or polydentate Lewis base, preferably L′ isreversibly coordinated to the metal complex such that it may bedisplaced by an olefin monomer, more preferably L′ is a monodentateLewis base;

1′ is a number greater than zero indicating the number of Lewis basemoieties, L′, and

Ar^(f) independently each occurrence is an anionic ligand group;preferably Ar^(f) is selected from the group consisting of halide, C₁₋₂₀halohydrocarbyl, and Q¹ ligand groups, more preferably Ar^(f) is afluorinated hydrocarbyl moiety of from 1 to 30 carbon atoms, mostpreferably Ar^(f) is a fluorinated aromatic hydrocarbyl moiety of from 6to 30 carbon atoms, and most highly preferably Ar^(f) is aperfluorinated aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms.

Examples of the foregoing Group 13 metal salts are alumiciniumtris(fluoroaryl)borates or gallicinium tris(fluoroaryl)boratescorresponding to the formula:[M″Q¹ ₂L′_(1′)]⁺(Ar^(f) ₃BQ²)⁻,wherein M″ is aluminum or gallium; Q¹ is C₁₋₂₀ hydrocarbyl, preferablyC₁₋₈ alkyl; Ar^(f) is perfluoroaryl, preferably pentafluorophenyl; andQ² is C₁₋₈ alkyl, preferably C₁₋₈ alkyl. More preferably, Q¹ and Q² areidentical C₁₋₈ alkyl groups, most preferably, methyl, ethyl or octyl.

The foregoing activating cocatalysts may also be used in combination. Anespecially preferred combination is a mixture of atri(hydrocarbyl)aluminum or tri(hydrocarbyl)borane compound having from1 to 4 carbons in each hydrocarbyl group or an ammonium borate with anoligomeric or polymeric alumoxane compound.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:1000 to 1:1. Alumoxane, when used by itself as an activatingcocatalyst, is employed in large quantity, generally at least 100 timesthe quantity of metal complex on a molar basis.Tris(pentafluorophenyl)borane, where used as an activating cocatalyst isemployed in a molar ratio to the metal complex of form 0.5:1 to 10:1,more preferably from 1:1 to 6:1 most preferably from 1:1 to 5:1. Theremaining activating cocatalysts are generally employed in approximatelyequimolar quantity with the metal complex.

The catalysts, whether or not supported in any suitable manner, may beused to polymerize ethylenically unsaturated monomers having from 2 to100,000 carbon atoms either alone or in combination. Preferred additionpolymerizable monomers for use herein include olefins, diolefins andmixtures thereof. Preferred olefins are aliphatic or aromatic compoundscontaining vinylic unsaturation as well as cyclic compounds containingethylenic unsaturation. Examples of the latter include cyclobutene,cyclopentene, norbornene, and norbornene derivatives that aresubstituted in the 5- and 6-positions with C₁₋₂₀ hydrocarbyl groups.Preferred diolefins are C₄₋₄₀ diolefin compounds, including ethylidenenorbornene, 1,4-hexadiene, norbornadiene, and the like. The catalystsand processes herein are especially suited for use in preparation ofethylene/1-butene, ethylene/1-hexene, ethylene/styrene,ethylene/propylene, ethylene/1-pentene, ethylene/4-methyl-1-pentene andethylene/1-octene copolymers as well as terpolymers of ethylene,propylene and a nonconjugated diene, such as, for example, EPDMterpolymers.

Most preferred monomers include the C₂₋₂₀ α-olefins, especiallyethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, long chainmacromolecular α-olefins, and mixtures thereof. Other preferred monomersinclude styrene, C₁₋₄ alkyl substituted styrene, ethylidenenorbornene,1,4-hexadiene, 1,7-octadiene, vinylcyclohexane, 4-vinylcyclohexene,divinylbenzene, and mixtures thereof with ethylene. Long chainmacromolecular α-olefins are vinyl terminated polymeric remnants formedin situ during continuous solution polymerization reactions. Undersuitable processing conditions such long chain macromolecular units arereadily polymerized into the polymer product along with ethylene andother short chain olefin monomers to give small quantities of long chainbranching in the resulting polymer.

Preferred monomers include a combination of ethylene and one or morecomonomers selected from monovinyl aromatic monomers,4-vinylcyclohexene, vinylcyclohexane, norbornadiene,ethylidene-norbornene, C₃₋₁₀ aliphatic α-olefins (especially propylene,isobutylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,and 1-octene), and C₄₋₄₀ dienes. Most preferred monomers are mixtures ofethylene and styrene; mixtures of ethylene, propylene and styrene;mixtures of ethylene, styrene and a nonconjugated diene, especiallyethylidenenorbornene or 1,4-hexadiene, and mixtures of ethylene,propylene and a nonconjugated diene, especially ethylidenenorbornene or1,4-hexadiene.

In general, the polymerization may be accomplished at conditions wellknown in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions, that is, temperatures from 0-250° C.,preferably 30 to 200° C. and pressures from atmospheric to 10,000atmospheres. Suspension, solution, slurry, gas phase, solid state powderpolymerization or other process condition may be employed if desired. Asupport, especially silica, alumina, or a polymer (especiallypoly(tetrafluoroethylene) or a polyolefin) may be employed, anddesirably is employed when the catalysts are used in a gas phasepolymerization process. The support is preferably employed in an amountto provide a weight ratio of catalyst (based on metal):support from1:10⁶ to 1:10³, more preferably from 1:10⁶ to 1:10⁴.

In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹²:1 to 10⁻¹:1,more preferably from 10⁻⁹:1 to 10⁻⁵:1.

Suitable solvents use for solution polymerization are liquids that aresubstantially inert under process conditions encountered in their usage.Examples include straight and branched-chain hydrocarbons such asisobutane, butane, pentane, hexane, heptane, octane, and mixturesthereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, and alkyl-substituted aromatic compounds such as benzene,toluene, xylene, and ethylbenzene. Suitable solvents also include liquidolefins which may act as monomers or comonomers.

The catalysts may be utilized in combination with at least oneadditional homogeneous or heterogeneous polymerization catalyst in thesame reactor or in separate reactors connected in series or in parallelto prepare polymer blends having desirable properties. An example ofsuch a process is disclosed in WO 94/00500.

The catalyst composition may be prepared as a homogeneous catalyst byaddition of the requisite components to a solvent or diluent in whichpolymerization will be conducted. The catalyst composition may also beprepared and employed as a heterogeneous catalyst by adsorbing,depositing or chemically attaching the requisite components on aninorganic or organic particulated solid. Examples of such solidsinclude, silica, silica gel, alumina, clays, expanded clays (aerogels),aluminosilicates, trialkylaluminum compounds, and organic or inorganicpolymeric materials, especially polyolefins. In a preferred embodiment,a heterogeneous catalyst is prepared by reacting an inorganic compound,preferably a tri(C₁₋₄ alkyl)aluminum compound, with an activatingcocatalyst, especially an ammonium salt of ahydroxyaryl(trispentafluoro-phenyl)borate, such as an ammonium salt of(4-hydroxy-3,5-ditertiarybutylphenyl)tris-(pentafluorophenyl)borate or(4-hydroxyphenyl)-tris(pentafluorophenyl)borate. This activatingcocatalyst is deposited onto the support by coprecipitating, imbibing,spraying, or similar technique, and thereafter removing any solvent ordiluent. The metal complex is added to the support, also by adsorbing,depositing or chemically attaching the same to the support, eithersubsequently, simultaneously or prior to addition of the activatingcocatalyst.

When prepared in heterogeneous or supported form, the catalystcomposition is employed in a slurry or gas phase polymerization. As apractical limitation, slurry polymerization takes place in liquiddiluents in which the polymer product is substantially insoluble.Preferably, the diluent for slurry polymerization is one or morehydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butane may be used in whole orpart as the diluent. Likewise, the α-olefin monomer or a mixture ofdifferent α-olefin monomers may be used in whole or part as the diluent.Most preferably, at least a major part of the diluent comprises theα-olefin monomer or monomers to be polymerized. A dispersant,particularly an elastomer, may be dissolved in the diluent utilizingtechniques known in the art, if desired.

At all times, the individual ingredients as well as the recoveredcatalyst components must be protected from oxygen and moisture.Therefore, the catalyst components and catalysts must be prepared andrecovered in an oxygen and moisture free atmosphere. Preferably,therefore, the reactions are performed in the presence of an dry, inertgas, such as, for example, nitrogen.

The polymerization may be carried out as a batchwise or a continuouspolymerization process. A continuous process is preferred, in whichevent catalyst, ethylene, comonomer, and optionally solvent, arecontinuously supplied to the reaction zone, and polymer productcontinuously removed therefrom.

Without limiting in any way the scope of the invention, one means forcarrying out such a polymerization process is as follows: In astirred-tank reactor, the monomers to be polymerized are introducedcontinuously, together with solvent and an optional chain transferagent. The reactor contains a liquid phase composed substantially ofmonomers, together with any solvent or additional diluent and dissolvedpolymer. If desired, a small amount of a “H”-branch inducing diene suchas norbornadiene, 1,7-octadiene or 1,9-decadiene may also be added.Catalyst and cocatalyst are continuously introduced in the reactorliquid phase. The reactor temperature and pressure may be controlled byadjusting the solvent/monomer ratio, the catalyst addition rate, as wellas by cooling or heating coils, jackets or both. The polymerization rateis controlled by the rate of catalyst addition. The ethylene content ofthe polymer product is determined by the ratio of ethylene to comonomerin the reactor, which is controlled by manipulating the respective feedrates of these components to the reactor. The polymer product molecularweight is controlled, optionally, by controlling other polymerizationvariables such as the temperature, monomer concentration, or by thepreviously mention chain transfer agent, such as a stream of hydrogenintroduced to the reactor, as is well known in the art. The reactoreffluent is contacted with a catalyst kill agent such as water. Thepolymer solution is optionally heated, and the polymer product isrecovered by flashing off gaseous monomers as well as residual solventor diluent at reduced pressure, and, if necessary, conducting furtherdevolatilization in equipment such as a devolatilizing extruder. In acontinuous process the mean residence time of the catalyst and polymerin the reactor generally is from about 5 minutes to 8 hours, andpreferably from 10 minutes to 6 hours.

Ethylene homopolymers and ethylene/α-olefin copolymers are particularlysuited for preparation according to the invention. Generally suchpolymers have densities from 0.85 to 0.96 g/ml. Typically the molarratio of α-olefin comonomer to ethylene used in the polymerization maybe varied in order to adjust the density of the resulting polymer. Whenproducing materials with a density range of from 0.91 to 0.93 thecomonomer to monomer ratio is less than 0.2, preferably less than 0.05,even more preferably less than 0.02, and may even be less than 0.01. Inthe above polymerization process hydrogen has been found to effectivelycontrol the molecular weight of the resulting polymer. Typically, themolar ratio of hydrogen to monomer is less than about 0.5, preferablyless than 0.2, more preferably less than 0.05, even more preferably lessthan 0.02 and may even be less than 0.01.

Highly desirably the present catalyst compositions have been found to behighly effective in the preparation of the foregoing ethylene copolymershaving an extremely low weight average molecular weight less than100,000, preferably less than 50,000; a high comonomer incorporationgreater than 5 weight percent, preferably greater than 10 weight percent(based on total polymer weight), and sufficient catalyst efficiency suchthat the polymerization can be conducted at solution polymerizationtemperatures from 95 to 160° C., preferably from 100 to 155° C., withcatalyst efficiencies greater than 400,000 g polymer/g Ti, preferablygreater than 1×10⁶ g polymer/g Ti. Even more surprising, the foregoingcopolymers are readily prepared using extremely low levels of hydrogenor other separately added chain transfer agent. In particular, the molarratio of hydrogen to monomer is desirably less than 0.01.

More particularly, the resulting copolymers consisting essentially ofethylene and one or more C₄₋₁₀ α-olefins are low molecular weightpolymers or waxes having a melt index, MI, greater than 10, preferablygreater than 100, or even oils. The oils find particular use asviscosity modifying additives for lubricants. The resulting copolymersof ethylene, propylene, and optionally one or more of norbornadiene,ethylidene-norbornene, or a C₄₋₄₀ diene as well as the copolymers ofethylene, a C₄₋₁₀ α-olefin, and one or more of norbornadiene,ethylidene-norbornene, or a C₄₋₄₀ diene are low molecular elastomers orthey are tackifiers or extenders for use in adhesive formulations,desirably having a Mooney viscosity from 0.01 to 10, preferably from 0.1to 10.

EXAMPLES

It is understood that the present invention is operable in the absenceof any component which has not been specifically disclosed. Thefollowing examples are provided in order to further illustrate theinvention and are not to be construed as limiting. Unless stated to thecontrary, all parts and percentages are expressed on a weight basis. Theterm “overnight”, if used, refers to a time of approximately 16-18hours, “room temperature”, if used, refers to a temperature of about20-25° C., and “mixed alkanes” refers to a mixture of hydrogenatedpropylene oligomers, mostly C₆-C₁₂ isoalkanes, available commerciallyunder the trademark Isopar E™ from ExxonMobil Chemicals Inc.

All syntheses and manipulations of air-sensitive materials were carriedout in an inert atmosphere (nitrogen or argon) glove box. Solvents werefirst saturated with nitrogen and then dried by passage throughactivated alumina and Q-5™ catalyst prior to use. Deuterated NMRsolvents were dried over sodium/potassium alloy and filtered prior touse. NMR spectra were recorded on a Varian INOVA 300 (FT 300 MHz, ¹H; 75MHz, ¹³C) spectrometer. Chemical shifts for ¹H and ¹³C spectra werereferenced to internal solvent resonances and are reported relative totetramethylsilane. Mass spectra were recorded on a VG Autospec (S/NV190) mass spectrometer. Coupling constants are reported in hertz (Hz).The 3,4-diphenyl-3-cyclopenten-1-ol was prepared according to literatureprocedure—Corey, E. J.; Uda, H. J. Am. Chem. Soc. 1963, 85, 1788-1792.

Melt Index values are determined according to ASTM D-1238, 190° C./2.16kg.

Mooney Viscosities are determined according to ASTM D1646-94, ML(1+4) at125° C.

Example 1dichloro[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-3,4-diphenyl-2,4-cyclopentadien-1-yl]silanaminato(2-)-κN]-titanium

A) Preparation of 3,4-diphenyl-3-cyclopentene-1-sulfonyl chloride.

3,4-Diphenyl-3-cyclopenten-1-ol (5.91 g) was dissolved in the mixture of70 mL of methylene chloride and 50 mL of pyrridine. To this reactionmixture was added 4 mL of CH₃SO₃Cl. After stirring overnight andreaction mixture was washed with 1 M of HCl, H₂O and NaHCO₃. Solutionwas dried over Mg₂SO₄ and then filtered. Solvent removal gave brownsolid. About 8 mL of ethyl acetate was added followed by 150 mL ofhexane producing off-white crystalline solid). After stirring overnightsolid was collected on the frit, washed with 10 mL of hexane and thendried under reduced pressure to give 4.0 g of product.

¹H (CDCl₃) δ 3.07 (s, 3H), 3.21 (dd, 2H, ²J_(H-H)=16.5 Hz, ³J_(H-H)=2.4Hz), 3.40 (dd, 2H, ²J_(H-H)=16.8 Hz, ³J_(H-H)=6.6 Hz), 5.50 (m, 1H),7.22 (m, 10H).

¹³C (CDCl₃) δ 38.49, 45.64, 79.21, 127.23, 128.04, 128.20, 133.82,136.45.

HRMS (EI): calculated for C₁₈H₁₈O₃S 314.0977 found 314.0970.

B) Preparation of 1-(4-bromo-2-phenyl-1-cyclopenten-1-yl)benzene

To a mixture of 3,4-diphenyl-3-cyclopentene-1-sulfonyl chloride (4 g)and 3 g of LiBr was added 70 mnL of acetone. Reaction mixture wasstirred under reflux for 2.5 hr. Solvent was removed under reducedpressure and the residue was extracted with 60 mL of methylene chloride.Solution was filtered and solvent was removed under reduced pressuregiving 3.1 g of product as brown-yellow solid.

¹H (CDCl₃) δ 3.35 (dd, 2H, ²J_(H-H)=16.2 Hz, ³J_(H-H)=3.6 Hz), 3.58 (dd,2H, ²J_(H-H)=16.2 Hz, ³J_(H-H)=6.6 Hz), 4.78 (m, 1H), 7.23 (m, 10H).

¹³C (CDCl₃) δ 46.97, 50.21, 127.13, 128.05, 128.21, 135.15, 136.79.

HRMS (EI): calculated for C₁₇H₁₅Br 298.0357 found 298.0338.

C) Preparation of (2,3-diphenyl-2,4-cyclopentadien-1-yl)potassium

To 2.93 g (9.79 mmol) of 1-(4-bromo-2-phenyl-1-cyclopenten-1-yl)benzenedissolved in 50 mL of toluene was added 4.10 g (20.6 mmol) of KN(TMS)₂dissolved in 60 mL of toluene within 5 minutes. Within minutes yellowprecipitate appeared. After stirring for 7 hours the solid was collectedon the frit, washed with hexane and dried under reduced pressure to give3.86 g of product.

¹H (THF-d⁸) δ 5.65 (t, 1H, ³J_(H-H)=3.3 Hz), 5.79 (d, 2H, ³J_(H-H)=3.3Hz), 6.74 (t, 2H, ³J_(H-H)=7.5 Hz, para), 6.94 (t, 4H, ³J_(H-H)=7.5 Hz,meta), 7.18 (d, 4H, ³J_(H-H)=7.5 Hz, ortho).

¹³C (THF-d⁸) δ 108.01, 110.24, 119.64, 121.97, 128.00, 128.25, 143.59.

HRMS (EI): calculated for C₁₇H₁₃K 256.0654 found 256.0688.D) Preparation ofN-(tert-butyl)(3,4-diphenyl-2,4-cyclopentadien-1-yl)dimethylsilanamine

The solid (2,3-diphenyl-2,4-cyclopentadien-1-yl)potassium was partlydissolved in 50 mL of THF and was added to 12.64 g (97.93 mmol) ofMe₂SiCl₂ dissolved in 40 mL of THF and 80 mL of ether. After stirringfor 1 hr solvent was removed under reduced pressure and the residue waspartly dissolved in 140 mL of toluene. To this solution was added 2.16mL of NH₂-t-Bu and the reaction mixture was stirred overnight. Theresulting solution was filtered and solvent was removed from thefiltrate to leaving 2.67 g of orange thick oil.

HRMS (EI): calculated for C₂₃H₂₉NSi 347.2069 found 347.2070

E) Preparation of dichloro[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-3,4-diphenyl-2,4-cyclopentadien-1-yl]silanaminato(2-)-κN]-titanium.

TheN-(tert-butyl)(3,4-diphenyl-2,4-cyclopentadien-1-yl)dimethylsilanamine(2.331 g, 6.71 mmol) and Ti(NMe₂)₄ 1.503 g, 6.71 mmol was dissolved in50 mL of octane. Reaction mixture was refluxed overnight. The colorchanged from orange to deep red. Solvent was removed under reducedpressure to give thick red oil (3.229 g). Proton NMR showed formation ofthe desired bis(amido) complex in about 75 percent yield. To a 3.229 gof the red oil dissolved in 40 mL of toluene was added 8.6 g ofMe₂SiCl₂. After stirring for 2 days solvent was removed under reducedpressure leaving dark solid. Hexane (50 mL) was added and the mixturewas stirred for 3 hours. Green-yellow solid was collected on the frit,washed with cold hexane (20 mL) and dried under reduced pressure to give1.66 g of product. Yield was 75 percent. The complex (0.71 g) wasdissolved in 10 mL of toluene followed by 50 mL of hexane. After 2minutes solution was filtered and put aside at room temperature. After afew minutes yellow crystals appeared. After 5 hours at room temperatureadditional crystals appeared and the solution was put into a −27° C.freezer overnight. Solvent was decanted and the crystals were washedwith 15 mL of cold hexane to give 512 mg of product.

¹H (C₆D₆) δ 0.32 (s, 6H, Si(CH₃)₃), 1.42 (s, 9H, C(CH₃)₃), 6.51 (s, 2H,H2), 702 (m, 6H), 7.54 (m, 4H).

¹³C{¹H} (C₆D₆) δ −0.10 (Si(CH₃)₃), 32.57 (C(CH₃)₃), 64.46 (C(CH₃)₃),110.00 (C1), 126.27, 128.38, 128.72, 130.13, 133.98, 141.37.

HRMS (EI, (M-CH₃)⁺): calculated for C₂₂H₂₂NSiTiCl₂ 448.0534 found448.0534.

Elemental Analysis. Calculated for C₂₃H₂₅NSiTiCl₂: C, 59.49; H, 5.86; N,3.02. Found: C, 59.25; H, 5.95; N, 3.42.

Example 2[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-3,4-diphenyl-2,4-cyclopentadien-1-yl]silanaminato(2-)-κN]-dimethyl-titanium

A) Preparation of[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-3,4-diphenyl-2,4-cyclopentadien-1-yl]silanaminato(2-)-κN]-dimethyl-titanium.

In the drybox 0.41 g (0.89 mmol) ofdichloro[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-3,4-diphenyl-2,4-cyclopentadien-1-yl]silanaminato(2-)-κN]-titaniumcomplex was dissolved in 30 ml of toluene. To this solution 1.2 mL (1.91mmol) of MeLi (1.6 M in ether) was added dropwise while stirring over a1 minute period. After the addition of MeLi was completed, the solutionwas stirred for 45 min. Toluene was removed under reduced pressure andthe residue extracted with 35 mL of hot hexane. Solution was filteredhot and put into a −27 ° C. freezer overnight. Solvent was decanted andthe yellow crystals were washed with cold hexane and then dried underreduced pressure to give 272 mg of product. Yield was 74.5 percent.

¹H NMR (C₆D₆) δ 0.34 (s, 6H, Si(CH₃)₃), 0.78 (s, 6H, Ti(CH₃)₃), 1.56 (s,9H, C(CH₃)₃), 6.18 (s, 2H, H2), 7.04 (m, 2H, para), 7.08 (m, 2H, meta),7.49 (m, 4H, ortho).

¹³C{¹H} (C₆D₆) δ 0.85 (Si(CH₃)₃), 34.54 (C(CH₃)₃), 56.27 (q,¹J_(C-H)=120.06 Hz, Ti(CH₃)₃), 59.68 (C(CH₃)₃), 104.88 (C1), 122.80(C2), 127.56 (para), 128.49 (meta), 129.55 (ortho), 135.39, 135.90.

HRMS (EI, (M-CH₃)⁺): calculated for C₂₄H₃₀NSiTi 408.1627 found 408.1624.

Elemental Analysis. Calculated for C₂₅H₃₃NSiTi: C, 70.90; H, 7.85; N,3.31. Found: C, 70.64; H, 7.91; N, 3.06.

Polymerizations

Ethylene/1-Octene Polymerization Conditions I

All liquid and gas feeds were passed through columns of alumina and adecontaminant (Q-5™ catalyst available from Englehardt Chemicals Inc.)prior to introduction into the reactor. Catalyst components are handledin a glovebox containing an atmosphere of argon or nitrogen. A stirred2.0 liter reactor is charged with 640 g of mixed alkanes solvent and 150g of 1-octene comonomer. Hydrogen (20 psi, 170 kPa) is added bydifferential pressure expansion from a 75 mL addition tank. The reactoris heated to 100° C. and saturated with ethylene at 500 psig (3.4 MPa).Metal complex as dilute toluene solution and cocatalyst as dilutesolutions in toluene or methycyclohexane were mixed in a 1:1 molar ratioand transferred to a catalyst addition tank and injected into thereactor. The cocatalyst was methyldi(octadecyl)ammoniumtetrakis(pentafluoro-phenyl)borate (MDBP), the ammonium cation of whichis derived from a mixture of amines available commercially as methylbis(tallow)amine. The polymerization conditions were maintained for 15minutes with ethylene added on demand. The resulting solution wasremoved from the reactor, quenched with isopropyl alcohol, andstabilized by addition of a toluene solution containing about 67 mg/100g polymer of a hindered phenol antioxidant (Irganox™ 1010 from CibaGeigy Corporation) and about 133 mg/100 g polymer of a phosphorusstabilizer (Irgafos™ 168 from Ciba Geigy Corporation).

Between sequential polymerization runs, a wash cycle was conducted inwhich 850 g of mixed alkanes was added to the reactor and the reactorwas heated to 150° C. The reactor was then emptied of the heated solventimmediately before beginning a new polymerization run.

A polymer according to the invention and a comparison polymer wererecovered by drying in a vacuum oven programmed to reach 140° C. over aperiod of about 20 hours. Density values are derived by determining thepolymer's mass when in air and when immersed in methylethyl ketone.Results are contained in Table 1.

TABLE 1 Ethylene/Octene Polymerization Results Catalyst Yield EfficiencyDensity Melt Run μmoles (g) (g/μg Ti) (g/mL) Index Mw MWD 1* ID¹ 48.422.6 0.877 0.06 246,047 2.06 (0.05) 2  Ex. 2 28.0 20.0 0.864 >100 27,609 2.95 (0.05) *comparative, not an example of the invention¹(dimethyl(N-(tert-butyl)-1,1-dimethyl-1-((1,2,3,3a,8a-η)-1,5,6,7-tetrahydro-2-methyl-s-indacen-1-yl)-silanaminato(2-)-κN)-titanium)prepared as outlined in WO98/27103 2. melt index as determined bymicromelt technique, equivalent to ASTM-D-1238, condition F.Ethylene/1-Octene/Ethylidenenorbornene Polymerization Conditions

All liquid feeds except ethylidenenorbornene (ENB) and gas feeds werepassed through columns of alumina and a decontaminant (Q-5™ catalystavailable from Englehardt Chemicals Inc.) prior to introduction into thereactor. ENB was passed through a short column (3×10 cm) of aluminaprior to introduction to the reactor. Catalyst components are handled ina glovebox containing an atmosphere of argon or nitrogen. A stirred 2.0liter reactor is charged with about 640 g of mixed alkanes solvent, 150g of 1-octene and 16 g of ENB. Hydrogen (20 psi, 140 kPa) is added bydifferential pressure expansion from a 75 mL addition tank. The reactoris heated to 100° C. and saturated with ethylene at 500 psig (3.5 MPa).Metal complex as dilute toluene solution and cocatalyst as dilutesolutions in toluene were mixed in a 1:1 molar ratio and transferred toa catalyst addition tank and injected into the reactor. The cocatalystwas methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl)borate(MDBP), the ammonium cation of which is derived from a mixture of aminesavailable commercially as methyl bis(tallow)amine. The polymerizationconditions were maintained for 15 minutes with ethylene added on demand.The resulting solution was removed from the reactor, quenched withisopropyl alcohol, and stabilized by addition of a toluene solutioncontaining about 67 mg/100 g polymer of a hindered phenol antioxidant(Irganox™ 1010 from Ciba Geigy Corporation) and about 133 mg/100 gpolymer of a phosphorus stabilizer (Irgafos™ 168 from Ciba GeigyCorporation).

Between sequential polymerization runs, a wash cycle was conducted inwhich 850 g of mixed alkanes was added to the reactor and the reactorwas heated to 130° C. The reactor was then emptied of the heated solventimmediately before beginning a new polymerization run.

Polymers were recovered by drying in a vacuum oven set at 140° C. forabout 20 hours. GPC results are determined by standard methods and arereported relative to a polystyrene/polyethylene universal calibration.The percent ethylene, 1-octene and ENB for the polymer and a comparisonpolymer were determined by IR spectroscopic analysis. Results arecontained in Table 2.

TABLE 2 Ethylene/Octene/ENB Polymerization Results Viscosity CatalystYield Efficiency ML % % % Run μmoles (g) (g/μg Ti) (1 + 4) ethyleneoctene ENB 3* ID¹ 92.5 2.03 125 75.4 20.3 4.4 (0.95) 4  Ex. 2 61.5 1.35<2 70.5 27.2 2.5 (0.95) *comparative, not an example of the invention¹(dimethyl(N-(tert-butyl)-1,1-dimethyl-1-((1,2,3,3a,8a-η)-1,5,6,7-tetrahydro-2-methyl-s-indacen-1-yl)-silanaminato(2-)-κN)-titanium)prepared as outlined in WO98/27103 2. melt index as determined bymicromelt technique, equivalent to ASTM-D-1238, condition F.Ethylene/Propylene/Ethylidenenorbornene Polymerization Conditions

All liquid feeds except ethylidenenorbornene (ENB) and gas feeds werepassed through columns of alumina and a decontaminant (Q-5™ catalystavailable from Englehardt Chemicals Inc.) prior to introduction into thereactor. ENB was passed through a short column (3×10 cm) of aluminaprior to introduction to the reactor. Catalyst components are handled ina glovebox containing an atmosphere of argon or nitrogen. A stirred 2.0liter reactor is charged with 780 g of mixed alkanes solvent, 16 g ofENB and hydrogen (20 psi, 140 kPa) is added by differential pressureexpansion from a 75 mL addition tank. The reactor is then charged with120 g of propylene and heated to 100° C. and saturated with ethylene at450 psig. Metal complex as dilute toluene solution and cocatalyst asdilute solutions in toluene were mixed in a 1:1 molar ratio andtransferred to a catalyst addition tank and injected into the reactor.The cocatalyst was methyldi(octadecyl)ammoniumtetrakis(pentafluoro-phenyl)borate (MDBP), the ammonium cation of whichis derived from a mixture of amines available commercially as methylbis(tallow)amine. The polymerization conditions were maintained for 15minutes with ethylene added on demand. The resulting solution wasremoved from the reactor, quenched with isopropyl alcohol, andstabilized by addition of a toluene solution containing about 67 mg/100g polymer of a hindered phenol antioxidant (Irganox™ 1010 from CibaGeigy Corporation) and about 133 mg/100 g polymer of a phosphorusstabilizer (Irgafos™ 168 from Ciba Geigy Corporation).

Between sequential polymerization runs, a wash cycle was conducted inwhich 850 g of mixed alkanes was added to the reactor and the reactorwas heated to 130° C. The reactor was then emptied of the heated solventimmediately before beginning a new polymerization run.

Polymers were recovered by drying in a vacuum oven set at 140° C. forabout 20 hours. GPC results are determined by standard methods and arereported relative to a polystyrene/polyethylene universal calibration.The percent ethylene, propylene and ENB for the polymer and a comparisonpolymer were determined by IR spectroscopic analysis. Results arecontained in Table 3.

TABLE 3 Ethylene/Propylene/ENB Polymerization Results Viscosity CatalystYield Efficiency ML % % pro- % Run μmoles (g) (g/μg Ti) (1 + 4) ethylenepylene ENB 5* ID¹ 48.4 0.72 105 46.1 45.5 8.0 (1.4) 6  Ex. 2 28.0 0.42 547.4 47.3 5.6 (1.4) *comparative, not an example of the invention¹(dimethyl(N-(tert-butyl)-1,1-dimethyl-1-((1,2,3,3a,8a-η)-1,5,6,7-tetrahydro-2-methyl-s-indacen-1-yl)-silanaminato(2-)-κN)-titanium)prepared as outlined in WO98/27103 2. melt index as determined bymicromelt technique, equivalent to ASTM-D-1238, condition F.Continuous Solution Polymerization

A series of ethylene/(α-olefin interpolymers are prepared in a 4 liter,oil jacketed, continuously stirred tank reactor (CSTR). A magneticallycoupled agitator provides mixing. The reactor is run liquid full at 475psi (3,275 kPa). Process flow is in at the bottom and out of the top. Aheat transfer oil is circulated through the jacket of the reactor toremove some of the heat of reaction. At the exit of the reactor is aflow meter that measured flow and solution density. All lines on theexit of the reactor are traced with 50 psi (300 kPa) steam andinsulated.

Mixed alkanes solvent and comonomer are supplied to the reactor at 30psi (200 kPa) pressure. The solvent feed to the reactors is measured bya mass flow meter. A variable speed diaphragm pump controls the solventflow rate and increases the solvent pressure to reactor pressure. Thecomonomer is metered by a mass flow meter and flow controlled by acontrol valve. The comonomer stream is mixed with the solvent stream atthe suction of the solvent pump and is pumped to the reactor with thesolvent. The remaining solvent is combined with ethylene and(optionally) hydrogen and delivered to the reactor. The ethylene streamis measured by a mass flow meter just prior to the flow control valve.Three flow meter/controllers (one limited to maximum 200 scm³/min. andtwo limited to a maximum of 100 scm³/min. flow) are used to deliverhydrogen into the ethylene stream at the outlet of the ethylene controlvalve.

The ethylene or ethylene/hydrogen mixture is combined with thesolvent/comonomer stream at ambient temperature. The temperature of thesolvent/monomer stream entering the bottom of the reactor is controlledwith two heat exchangers.

In an inert atmosphere box, a solution of the transition metal compoundis prepared by mixing the appropriate volumes of concentrated solutionswith additional solvent to provide the final catalyst solution of knownconcentration and composition. This solution is transferred undernitrogen to a pressure vessel attached to a high-pressure metering pumpfor transport to the polymerization reactor.

In the same inert atmosphere box, solutions of a cocatalyst mixture,MDBP and modified methylalumoxane (CAS 146905-79-10, MMAO Type 3A,available form Akzo Nobel) are prepared in mixed alkanes solvent andtransferred to separate pressure vessels. The molar ratio of Al to Ti(6.00) and B to Ti (1.25) are established by controlling the volumetricflow output using metering pumps attached to each pressure vessel andconnected to an inlet in the bottom of the reactor.

Polymerization is conducted at 150° C. and stopped with the addition ofcatalyst kill into the reactor product line after the meter measuringthe solution density. The reactor effluent stream then enters a postreactor heater that provides additional energy for solvent removal.Solvent is flash removed as the effluent exits the post reactor heaterand the pressure is released.

This flashed polymer next enters a hot oil jacketed devolatilizer whereapproximately 90 percent of the volatiles are removed from the polymer.The remaining polymer stream is condensed with a chilled water jacketedexchanger and then enters a glycol jacket solvent/ethylene separationvessel. Solvent is removed from the bottom of the vessel and ethylene isvented from the top. The quantity of vented ethylene is measured with amass flow meter. The devolatilized polymer exits the devolatilizerthrough a gear pump. The product is collected in lined pans and dried ina vacuum oven at 140° C. for 24 hr.

The polymers are stabilized with approximately 1000 ppm Irganox 1010 and2000 ppm Irgafos 168 stabilizers obtained from Ciba Geigy Corporation.Stabilizers are added in combination with the catalyst kill. Table 4summarizes the polymerization results.

TABLE 4 Continuous Ethylene/1-Octene Copolymerization Results C₈ H₂ C₂H₄Effi- Flow Flow Conver- ciency Visco- Den- (kg/ (scc/ sion (g poly./sity sity Run Cat. hr) min) (percent) μg Ti) (Pa · s) (g/cm³) 7* TC¹0.612 108 90.0 1.12 3.199 0.9034 8  Ex. 2 0.454 24 90.4 1.02 3.1320.9047 *comparative, not an example of the invention¹(N-(t-butyl)-1,1-dimethyl-1-(tetramethylcyclopentadienyl)silanaminato(2-)-κN)-titanium(II) 1,3-pentadiene

By comparison of the results of Table 4 it may be seen that lowmolecular weight copolymers having essentially equivalent properties canbe produced while employing much lower hydrogen levels according to thepresent invention.

E. Continuous Ethylene/Propylene/Ethylidene-norbornene Copolymerization

A series of ethylene/propylene/ethylidene-norbornene copolymers areprepared in a 6.8 L, oil jacketed, continuously stirred tank reactor(CSTR) under conditions substantially identical to those recited inpreparation D, excepting the comparison catalyst is(dimethyl(N-(tert-butyl)-1,1-dimethyl-1-((1,2,3,3a,8a-η)-1,5,6,7-tetrahydro-2-methyl-s-indacen-1-yl)-silanaminato(2-)-κN)-titanium)(ID), prepared as outlined in WO98/27103, and the molar ratio of Ti:B:Alemployed is 1:1.1:11. Comonomer content of the polymers are determinedby Fourier Transform IR analysis. Results are summarized in Table 5.

TABLE 5 Catalyst ID* Ex. 2 Temp ° C. 95 95 C₂H₄ Conversion (percent) 8585 Production Rate (kg/hr) 0.49 0.49 Ethylene (kg/hr) 0.39 0.39Propylene (kg/hr) 0.24 0.24 ENB (kg/hr) 0.026 0.026 Efficiency (gpolymer/μg Ti) 0.98 0.21 Hydrogen (scm³/min) 10.5 10.6 Mooney Viscosity22 <2 Percent C₂H₄ 69.2 68.7 Percent C₃H₆ 28.6 26.0 Percent ENB 2.2 5.3*Comparative, not an example of the invention

1. A polymerization process comprising contacting one or more additionpolymerizable monomers selected from the group consisting of ethyleneand one or more C₄₋₁₀ α-olefins under polymerization conditionsincluding a temperature from 95 to 160° C. with a catalyst compositioncomprising a metal complex corresponding to the formula:

wherein, Ar is an aryl group of from 6 to 30 atoms not countinghydrogen; R independently each occurrence is hydrogen, Ar, or a groupother than Ar selected from hydrocarbyl, trihydrocarbylsilyl,trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsiloxy,bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino,hydrocarbadiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino,hydrocarbadiylphosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R group having up to 40atoms not counting hydrogen atoms; M is titanium; Z′ is SiR⁶ ₂, CR⁶ ₂,SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂, BR⁶, BR⁶L″, or GeR⁶ ₂; Yis —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂; R⁵, independently eachoccurrence, is hydrocarbyl, trihydrocarbylsilyl, ortrihydrocarbylsilylhydrocarbyl, said R⁵ having up to 20 atoms other thanhydrogen, and optionally two R⁵ groups or R⁵ together with Y form a ringsystem; R⁶, independently each occurrence, is hydrogen, or a memberselected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl,halogenated aryl, —NR⁵ ₂, and combinations thereof, said R⁶ having up to20 non-hydrogen atoms, and optionally, two R⁶ groups form a ring system;L″ is a monodentate or polydentate Lewis base optionally bonded to R⁶; Xis hydrogen or a monovalent anionic ligand group having up to 60 atomsnot counting hydrogen; L independently each occurrence is a neutralligating compound having up to 20 atoms, other than hydrogen, andoptionally L and X are bonded together; X′ is a divalent anionic ligandgroup having up to 60 atoms other than hydrogen; z is 0, 1 or 2; x is 0,1, 2, or 3; l is a number from 0 to 2, and x′ is 0 or 1, to prepare apolymer having a melt index greater than 1.0 and a comonomerincorporation greater than 5 weight percent.
 2. A process according toclaim 1, wherein at least one R is selected from the group consisting ofAr.
 3. A process according to claim 2, wherein the cyclopentadienylgroup is substituted at the 3- and 4-position with an Ar group.
 4. Aprocess according to any one of claims 1-3, wherein: Ar is phenyl,naphthyl, 4-bisphenyl, 3-(N,N-dimethylamino)phenyl, 4-methoxyphenyl,4methylphenyl, pyrrol-1-yl, or 1-methylpyrrol-3-yl; R is hydrogen,methyl or Ar; X is chloride, methyl or benzyl; X′ is2,3-dimethyl-1,3-butenediyl; L is 1,3-pentadiene or1,4-diphenyl-1,3-butadiene; Y is —NR⁵—; Z′ is SiR⁶ ₂; R⁵ each occurrenceis independently hydrocarbyl; R⁶ each occurrence is independentlymethyl; x is 0 or 2; l is 0 or 1; and x′ is 0 or 1; with the provisothat: when x is 2, x′ is zero, and M is in the +4 formal oxidationstate, when x is 0 and x′ is 1, M is in the +4 formal oxidation state,and when x and x′ are both 0, l is 1, and M is in the +2 formaloxidation state.
 5. A process according to claim 1 wherein the metalcomplex is selected from the group consisting of:(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl, and(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,3-pentadiene.
 6. A process according to any one of claims 1-3which is a solution polymerization.
 7. A process according to claim 4which is a solution polymerization.
 8. A polymerization processcomprising contacting ethylene, propylene, and optionally one or more ofnorbornadiene, ethylidene-norbornene, or a C₄₋₄₀ diene or contactingethylene, a C₄₋₁₀ α-olefin, and one or more of norbornadiene,ethylidene-norbornene, or a C₄₋₄₀ diene under polymerization conditionsincluding a temperature from 95 to 160° C. with a catalyst compositioncomprising a metal complex corresponding to the formula:

wherein, Ar is an aryl group of from 6 to 30 atoms not countinghydrogen; R independently each occurrence is hydrogen, Ar, or a groupother than Ar selected from hydrocarbyl, trihydrocarbylsilyl,trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsiloxy,bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino,hydrocarbadiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino,hydrocarbadiylphosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R group having up to 40atoms not counting hydrogen atoms; M is titanium; Z′ is SiR⁶ ₂, CR⁶ ₂,SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂, BR⁶, BR⁶L″, or GeR⁶ ₂; Yis —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂; R⁵, independently eachoccurrence, is hydrocarbyl, trihydrocarbylsilyl, ortrihydrocarbylsilylhydrocarbyl, said R⁵ having up to 20 atoms other thanhydrogen, and optionally two R⁵ groups or R⁵ together with Y form a ringsystem; R⁶, independently each occurrence, is hydrogen, or a memberselected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl,halogenated aryl, —NR⁵ ₂, and combinations thereof, said R⁶ having up to20 non-hydrogen atoms, and optionally, two R⁶ groups form a ring system;L″ is a monodentate or polydentate Lewis base optionally bonded to R⁶; Xis hydrogen or a monovalent anionic ligand group having up to 60 atomsnot counting hydrogen; L independently each occurrence is a neutralligating compound having up to 20 atoms, other than hydrogen, andoptionally L and X are bonded together; X′ is a divalent anionic ligandgroup having up to 60 atoms other than hydrogen; z is 0, 1 or 2; x is 0,1, 2, or 3; l is a number from 0 to 2, and x′ is 0 or 1, to prepare apolymer having a Mooney Viscosity from 0.01 to 10 and a comonomerincorporation greater than 5 weight percent.
 9. A process according toclaim 8, wherein at least one R is selected from the group consisting ofAr.
 10. A process according to claim 8, wherein the cyclopentadienylgroup is substituted at the 3- and 4-position with an Ar group.
 11. Aprocess according to any one of claims 8-10, wherein: Ar is phenyl,naphthyl, 4-bisphenyl, 3-(N,N-dimethylamino)phenyl, 4-methoxyphenyl,4-methylphenyl, pyrrol-1-yl, or 1-methylpyrrol-3-yl; R is hydrogen,methyl or Ar; X is chloride, methyl or benzyl; X′ is2,3-dimethyl-1,3-butenediyl; L is 1,3-pentadiene or1,4-diphenyl-1,3-butadiene; Y is —NR⁵—; Z′ is SiR⁶ ₂; R⁵ each occurrenceis independently hydrocarbyl; R⁶ each occurrence is independentlymethyl; x is 0 or 2; l is 0 or 1; and x′ is 0 or 1; with the provisothat: when x is 2, x′ is zero, and M is in the +4 formal oxidationstate, when x is 0 and x′ is 1, M is in the +4 formal oxidation state,and when x and x′ are both 0, l is 1, and M is in the +2 formaloxidation state.
 12. A process according to claim 8 wherein the metalcomplex is selected from the group consisting of:(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl, and(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,3-pentadiene.
 13. A process according to any one of claims 8-10which is a solution polymerization.
 14. A process according to claim 12which is a solution polymerization.